Diazonium compounds



Patented Mar. 31, 1953 DIAZONIUM COMPOUNDS Wilhelm Seidenfaden and Franz Muris, Offenbach-on-the-Main,

Germany,

assignors to Naphtol-Chemie Offenbach, Offenbach-onthe-Main, Germany No Drawing. Application March 24, 1951, Serial No. 217,406. In Germany March 27, 1950 8 Claims. 1

This invention relates to a process for the manufacture of diazonium compounds made from 2- amino-azo compounds. 7

It is an object of this invention to provide for a process for the preparation of such diazonium compounds which are more readily soluble in water than the hitherto known diazonium compounds made from Z-amino-azo compounds.

It is another object of this invention to provide for a process for diazotizing 2-amino-azo compounds by using acids of a considerably lower concentration than the concentrations hitherto necessary for diazotizing Z-amino-azo compounds of the type used up to now for the preparation of such diazonium compounds.

This invention relates to the preparation of diazonium compounds made from 2-amino-azo compounds of the following general formula:

NHz (A) wherein at least on of the hydrogen atoms of the phenyl nucleus I is replaced by a substituent of the group consisting of Cl, N02, OCHs, CN, X stands for a member of the group consisting of alkyl, alkoxy and halogen, and Y stands for a member of the group consisting of hydrogen and alkyl, whereas Z stands for an alkyl radical.

This invention more particularly relates to the preparation of diazonium compounds made from Z-amino-azo compounds of the following general formula:

Y OCH:OON

H X1 CH:

l I Y Xn N=N O CHQC ON I Z Xm H NH: (B)

wherein X1 stands for a substituent of the group consisting of H, Cl, N02, OCHs, X11 stands for a substituent of the group consisting of H, N02, CN, Xm stands for a substituent of the group consisting of H, Cl, OCHs, at least one of the substituents X1, Xn and Xm standing for a substituent other than H; and wherein Y and Z stand for a substituent of the group consisting of CH3 and Cal-I5.

It is known to use as components for the manufacture of azo dyestuffs 2-amino-azo compounds of the following general formula:

wherein X stands for alkoxy, Y for alkyl, alkoxy or halogen and wherein the benzene nucleus I may contain substituents. These compounds can be diazotized only under energetic conditions, and the diazonium compounds so obtained are always of relatively low solubility.

In order to diazotize such bases it is necessary to work in highly concentrated hydrochloric or sulphuric acid or with the addition of solution promoters such, for example, as acetic acid. These methods necessitate the use of special measures, such as the removal of gases, for example hydrogen chloride gas, which are injurious to health and strongly corrosive, or the protection of the apparatus against the attack of concentrated sulphuric acid or nitrosyl-sulphuric acid, so that the process is not suitable for general application and is hardly economical.

Furthermore, in many cases the low solubility of the diazonium compounds renders difiicult their extensive application for the production of dyestuffs on the fibre, for example, as supplementary additions in working with standin baths or for the production of strong developing solutions such as are used in printing for producing deep tints.

Now we have found that Z-amino-azo compounds of the following general formula:

wherein at least one of the hydrogen atoms of the phenyl nucleus I is replaced by a substituent of the group consisting of Cl, N02, OCHa, CN, X stands for a member of the group consisting of alkyl, alkoxy and halogen, and Y stands for'a member of the group consisting of hydrogen and alkyl, whereas Z stands for an alkyl radical, can be diazotized already with moderately concentrated mineral acids, especially with hydrochloric acid, or with sulphuric acid or nitric acid.

For instance, hydrochloric acid may be used for diazotizing the said bases in such concentrations which do not evolve hydrogen chloride gas at ordinary temperature, i. e. having a con tent of about 15 to 20 per cent of HCl. Sulphuric acid, for instance, may be used in concentrations up to '75 or per cent of H2504. 7

It is evident that this possibility to carry out the diazotization process with acids of considerably lower concentrations than hitherto used for diazotizing comparable Z-amino-azo compounds, enables the diazotization to be made more economically and commercially wit greater ease.

. X Goa-COM used as starting materialscan.wbeiohtainem-zior example, in the following manner x v 1 9001120001! -f oomo0o1 3 NO 1 ii'NHz :aSince .lthe essential feature of .the invention consists -in replacing the-i-alkoxycroup of the hitherto "-used -:2eamino-.azo compounds by an oxyacetic-z acid*residue being 1 substituted in the rcarboxylic acid groupby-an ,alkylated amino group, the substitutionof the compounds de- -scribed:herein:may bezvaried in other directions '10 E3HTICDH5idB1flh16 extent without leaving the :scope; ofathis .invention.

r-For;v instance, instead of using .a dialkylamino substituted oxyacetic acid residue wherein both .alky1:groups'='are of-,.-the same constitution, one may use compounds havingtwo 1diiTerent alkyl groups in the amino group. There can also be usedunono-alkyl derivatives of the oxyacetic acid substituted Z-amino-azmcompound.

Likewise, the substitution of the phenyl nucleus I (Formula A) may be varied in addition to the examples given herein; it may also be unsubstituted.

'iIhe substituent X of Formula A may, for in- IStaIICB, be methylpr ethyl, methoxy orethoxy torn halogenratom, especially '01.

This "invention is "not restricted to the use of 'imineral acids inmoderate concentrations. It is "obvious that the same-bases can-be 'diazotized :also by applying stronger concentrations of the acids. However, it 'is-an "essential advantage of the new process that-the herein described new "2-amino-azo'compounds can be diazotized in much weaker concentrations of acids than the hitherto used 2-amino-azo compounds-substituted by *a 4-alkoxy group in meta-position to "the amino group to be diazotized. Besides, the "new diazonium compounds themselves are distinguished over the hitherto known "comparable compounds "by 'an essentially greater solubility which facilitates their application.

"The -followingexamp1es illustrate the invention, 'the'partsbeing by' weight unless otherwise :statedan'd the-relationship of parts by weight to partsby volume being the-sameas that of the kilogram to the litre:

Example 1 24 parts by volume of a solution of vsodium nitrite. f. 3O r. iperr cent .-.-strength 'l-areiadded drop- :iwisein the course of 30 iminutes while stirring well, to a suspension of 42.4 parts of finely ground 12 amino 5 methyl 4 nitro 2 chlor azobenzene-l-oxyacetic acid-diethylamide in 600 parts o'f hydrochloric acid of 17.7 per cent .stren theat. 1572010. After stirring for a further [2: hour'the.diazotization ceases, the diazo soluztiongisireedjrom a small amount of turbidity -by-;stirringi..it.;for;a short time with 3 parts of kieselguhr followed by filtering with suction. "lintothelresulting clear yellowish red diazo'solu- 'tion are runin the course of 30 minutes 19 parts .by volume of zinc chloride solution of 48 per cent strength, whereby the diazonium chloride-zinc chloride .douhlewsalt-is ,formed, andlthe .latter is isolated by filtering with suction sand .dried. 82 parts of the diazonium compound w.011? .the "formula:

are obtained having a purity l of .465 per; cent calculated on.the base havingcaflmolecular weight of 419.5, which representsa yield of '91,per.cent

of the theoretical yield. The. diazoniumucompound, so obtained hasoa. .solubility 0f,.-15 -.grams of. the base in l vlitre vof Water.

A comparable ,product which .Jcontains instead of the oxyacetic acid residue, a methoxy group, namely 2 amino 4 methoxy 5 methyl 4' nitro-=2-chlorazobenzene, can be diazotized satisfactorily only'with the use of times the quantity of hydrochloric acid of 25 per cent strength, and the diazonium chloride-zinc chloride double salt ihasasolubility of only 7.2 grams in .1 litre of water.

-A comparison ofthesolubilities of the corresponding diazonium chlorides .shows a similar result, .namely zangrams per litre in'lthe casenof the-compound as compared with 16 gramsperylitre in' the case ofthe compound .lQiHs 25 0 01120 OZN C ZnCla 2 I NOQ =N O'CH;

Example? tised well only with sodium nitrite solution in a azonium chloride is 15 grams in 1 litre of water.

mixture of hydrochloric acid and glacial acetic In the following table are given the solubiliacid or with nitrosyl sulphuric acid in concenties of further examples of diazonium compounds trated sulphuric acid. The solubility of its diprepared in accordance with the invention as azonium chloride-zinc chloride double salt is 8 5 compared with those of the comparable 4- grams in 1 litre of water and that of the dimethoxy-compounds.

Solubility in grams or base per litre the diazonlum the diazonium chloride-zinc chloride chloride double salt Diazonlum compound 0!:

CH: 20. 9 13. 0 /C:H5 rim-ON: 003.0 ON\ C 1H5 NH: as compared with:

NH: Diazonium compolmd cl: 7

01 CH: C m 14. 1 9. 0

a =N 0 CHzC 0N\ CzHa 1 NH:

as compared with:

411 I IHa Dlezonium compound of:

Cl C H; 23. 2 14. 0

| /C H: NOT-Oran OGHaOON\ CH: NHa as compared with:

NH; Diazonium compound 0!:

O CH: CH: 28. 6 17. 6

/C in; ON N= 0 0 H1O 0N\ cm 0 OH: NH: 5

as compared with:

O C Hz 0H; 8. 8 5. 6

CN N=N 0 CH:

O CH: NH:

Diazonium compound of:

O CH: CH: 39. 0 19. 8

0 5 NO. N= 0 CHzC ON 0 :H5 NH: as compared with:

0 C H: C H: 14. 0 8. 2 N0|C N= 0 cm cacao- 01 '7 We: claim Diazoniumzcompounds of. :the" class; consistl1ing-;.of .those:.;l1aving athe: followingggeneralior- .;mula

3 III 1N zwhereinaat leaistrone:of the hydrogen atoms of thejrihenyl nucleus I is replaced by a substituent .of-thegroupconsisting of Cl, N02, OCI-IaWCN, 2! stands for a member:of the group consisting of alkyl, alkoxy-and halogen, and Y stands for a member of the group consisting of hydrogenand alkyl, whereas Z stands for an-alkyl radical, and wherein R, is an anion of-a-mineral acid, and'the zinc chloride double salts of such compounds.

2. Diazonium compounds of the class consisting of those having the following general formula.

/Y N: omo ON wherein X1 stands for a substituent of the group consisting of H, Cl, N02, OCHs, Xn stands for a substituent of the group consisting of H, N02, 'CN, Xm stands for a substituent of'the group consisting of H, Cl, OCHa, at least one of the substituents X1, X11 and X111 standing for a substituent other than H; and wherein Y and Zstands for a substituent of the group consisting of- CH3 and CzHs; and wherein R, is an anion of a min .eral acid, and the zinc chloride double salts of '"such compounds.

3. Diazonium compounds of the classconsi'sting of those having the following general formula:

III N wherein Xrstands for a substituent of the group consisting of H, C1, N02, OCHs, and Y andiz standforz-the same substituent of the groupconrsistin xof CH3 and (321-15, and .the. zinc chloride double salts. of such compounds.

4- A .diazonium .compound -of :the .iollowing 5 structural .formula:

6. A diazonium compound of the following structural formula No, on; l /C2Ha "NO N= Ooom-ooN 01H; N-Cl Z1101, m

7. Al diazonium compound of the following structural formula C1115 "NOON=N OOHQ-GON C2Hs NCI Z1101: m N

40 8. A diazonium compound of the following structural formula:

| \oz s 0 CH2. C ON I WILHELM SEIDEN'FADEN. FRANZ MURIS.

ZIlClg 2 No references cited. 

4. A DIAZONIUM COMPOUND OF THE FOLLOWING STRUCTURAL FORMULA: 